Enzymatic Cascade Catalysis for the Synthesis of Multiblock and Ultrahigh‐Molecular‐Weight Polymers with Oxygen Tolerance

Abstract

Synthesis of well-defined multiblocka nd ultrahighmolecular-weight (UHMW) polymers has been ap erceived challenge for reversible-deactivation radical polymerization (RDRP). An even more formidable task is to synthesize these extreme polymers in the presence of oxygen. Anovel methodology involving enzymatic cascade catalysis is developed for the unprecedented synthesis of multiblock polymers in open vessels with direct exposure to air and UHMW polymers in closed vessels without prior degassing.T he success of this methodology relies on the extraordinary deoxygenation capability of pyranose oxidase (P2Ox) and the mild yet efficient radical generation by horseradish peroxidase (HRP). The facile and green synthesis of multiblockand UHMW polymers using biorenewable enzymes under environmentally benign and scalable conditions provides anew pathway for developing advanced polymer materials.

Chemo-enzymatic pathways toward pinene-based renewable materials

“…21 Over the last years, many studies have been devoted to the use of enzymes as mediators for different polymerization techniques. [22][23][24][25][26] Polymers from terpenes, or chemically modified terpenes, exhibit a wide range of molecular weights and thermal properties depending on the terpene structure/compo-sition and polymerization technique. 12,27 In the pursuit of novel polymeric materials, exploring the toolbox of terpenebased polymers holds great potential.…”

Protein-polymer bioconjugates via a versatile oxygen tolerant photoinduced controlled radical polymerization approach

“…Recently, seminal work by the groups of Boyer 39,40 , Matyjaszewski [41][42][43] and others [44][45][46][47] led to elegant approaches in which no external deoxygenation is required for the synthesis of well-defined polymers. Such systems typically employ enzymes (e.g., glucose oxidase) [48][49][50] , sacrificial substrates 43 , and/or increased concentrations of photocatalysts or reducing agents [51][52][53] to in situ consume oxygen prior to polymerization. However, the applicability of such systems in the synthesis of protein-polymer conjugates is currently limited, since external reducing agents and/or enzymes may significantly increase the complexity of the "grafting from" approach, affect protein integrity and render product isolation tedious.…”

Biocatalytic Hybrid Nanoparticles for Degassing and Stabilization of Single Electron Transfer-Living Radical Polymerization in Pickering emulsions

“…hydrazine), [10] [11] thus hampering the scale-up and transition from academia to industry of these controlled polymerization processes. To overcome this issue, notable works from the groups of Stevens [12][13][14] and Matyjaszweski, [15][16][17] among others [18][19][20][21] reported the use of oxidoreductase enzymes to deplete oxygen, thus giving rise to enzyme-degassed RDRP techniques.…”

“…[12] [13] So far, most of these systems have been applied in RAFT and ATRP of water-soluble monomers in aqueous media to retain the enzyme activity. [16][17][18][19][20] The polymerization of hydrophobic monomers remains scarcely explored, and is hitherto limited to ATRPmediated miniemulsion processes using soluble ionic surfactants such as dodecyl sulfate (SDS), [17] which could disrupt the activity of the enzyme at longer reactions times. [22] Indeed, some of these previous reported systems require the addition of sacri cial substrates (e.g.…”